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Secondary aerosol formation from photochemical aging of aircraft exhaust in a smog chamber

Field experiments were performed to investigate the effects of photo-oxidation on fine particle emissions from an in-use CFM56-2B gas turbine engine mounted on a KC-135 Stratotanker airframe. Emissions were sampled into a portable smog chamber from a rake inlet installed one-meter downstream of the engine exit plane of a parked and chocked aircraft. The chamber was then exposed to sunlight and/or UV lights to initiate photo-oxidation. Separate tests were performed at different engine loads (4, 7, 30, 85 %). Photo-oxidation created substantial secondary particulate matter (PM), greatly exceeding the direct PM emissions at each engine load after an hour or less of aging at typical summertime conditions. After several hours of photo-oxidation, the ratio of secondary-to-primary PM mass was on average 35 ± 4.1, 17 ± 2.5, 60 ± 2.2, and 2.7 ± 1.1 for the 4, 7, 30, and 85 % load experiments, respectively. The composition of secondary PM formed strongly depended on load. At 4 % load, secondary PM was dominated by secondary organic aerosol (SOA). At higher loads, the secondary PM was mainly secondary sulfate. A traditional SOA model that accounts for SOA formation from single-ring aromatics and other volatile organic compounds underpredicts the measured SOA formation by ~60 % at 4 % load and ~40 % at 85 % load. Large amounts of lower-volatiliy organic vapors were measured in the exhaust; they represent a significant pool of SOA precursors that are not included in traditional SOA models. These results underscore the importance of accounting for atmospheric processing when assessing the influence of aircraft emissions on ambient PM levels. Models that do not account for this processing will likely underpredict the contribution of aircraft emissions to local and regional air pollution.
Global and regional effects of the photochemistry of CH3O2NO2: evidence from ARCTAS

Using measurements from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) experiment, we show that methyl peroxy nitrate (CH3O2NO2) is present in concentrations of ~5–15 pptv in the springtime arctic upper troposphere. We investigate the regional and global effects of CH3O2NO2 by including its chemistry in the GEOS-Chem 3-D global chemical transport model. We find that at temperatures below 240 K inclusion of CH3O2NO2 chemistry results in decreases of up to ~20 % in NOx, ~20 % in N2O5, ~5 % in HNO3, ~2 % in ozone, and increases in methyl hydrogen peroxide of up to ~14 %. Larger changes are observed in biomass burning plumes lofted to high altitude. Additionally, by sequestering NOx at low temperatures, CH3O2NO2 decreases the cycling of HO2 to OH, resulting in a larger upper tropospheric HO2 to OH ratio. These results may impact some estimates of lightning NOx sources as well as help explain differences between models and measurements of upper tropospheric composition.
Observation of atmospheric aerosols at Mt. Hua and Mt. Tai in central and east China during spring 2009 – Part 1: EC, OC and inorganic ions

PM10 and size-segregated samples were simultaneously collected at Mt. Hua (2060 m a.s.l.) and Mt. Tai (1545 m a.s.l.) in central and east coastal China during spring, 2009 including an intensive dust storm event occurring on 24 April, and determined for EC, OC and inorganic ions. During the non-dust storm period particles, EC, OC and ions except for SO42− were 2–10 times more abundant at Mt. Tai than at Mt. Hua. SO42− (13 ± 7.1 μg m−3) at Mt. Hua was the dominant ion, followed by NO3− (5.0 ± 3.9 μg m−3), NH4+ (2.5 ± 1.3 μg m−3) and Ca2+ (1.6 ± 0.8 μg m−3). In contrast, at Mt. Tai NO3− was most abundant (20 ± 14 μg m−3), followed by SO42− (16 ± 13 μg m−3), NH4+ (12 ± 8.9 μg m−3) and Ca2+ (3.9 ± 2.1 μg m−3). The fact of NO3− exceeding over SO42− at Mt. Tai may suggest the changes in chemical composition of the atmosphere over east China due to sharply increasing vehicle emission. pH values of the water-extracts of PM10 samples indicate that at the two mountain sites aerosols transported from the south regions are more acidic than those from the north and more acidic at Mt. Tai than at Mt. Hua during the non-dust storm period. During the dust storm event particle mass, OC, Na+, K+, Mg2+ and Ca2+ at both sites increased by a factor of 1–9, while EC, NO3− and NH4+ decreased by 20–80 %. However, SO42− concentrations (13 ± 7.7 μg m−3 at Mt. Hua and 15 ± 5.6 μg m−3 at Mt. Tai, respectively) at the two sites during the episode were comparable and did not change significantly compared to those in the non-dust storm period, probably due to a similar level of free tropospheric SO2 in central and east China. Compared with those at Mt. Hua the coarse modes (>2.1 μm) of K+ and SO42− at Mt. Tai during the non-event period were more abundant and the coarse mode of NO3− was less abundant. When the dust storm was present all ions significantly moved toward coarse particles, except for NH4+, with a disappeared peak in fine mode (<2.1 μm) for NO3−. Linear regression for ion equivalents in fine particles indicates that ammonium exists in the forms of NH4NO3 and NH4HSO4 at Mt. Hua and NH4NO3 and (NH4)2SO4 at Mt. Tai during both the nonevent and the event periods. While the regression for coarse mode of Ca2+ suggests a close coupling of dust with nitrate during the nonevent time and with sulfate during the dust-storm period. pH values of the size-resolved samples further suggest that during the nonevent period most acidic particles at Mt. Hua are in the range of 0.7–1.1 μm, while those at Mt. Tai are in the range of 1.1–2.1 μm. Aerosols at both sites became alkaline during the event, but the Mt. Tai particles still showed a lower pH value.
Statistical dynamics of tropical wind in radiosonde data

Weibull distributions were fitted to wind speed data from radiosonde stations in the global tropics. A statistical theory of independent wind contributions was proposed to partially explain the shape parameter k obtained over Malay Peninsula and the wider Equatorial Monsoon Zone. This statistical dynamical underpinning provides some justification for using empirical Weibull fits to derive wind speed thresholds for monitoring data quality. The regionally adapted thresholds retain more useful data than conventional ones defined from taking the regional mean plus three standard deviations. The new approach is shown to eliminate reports of atypically strong wind over Malay Peninsula which may have escaped detection in quality control of global datasets as the latter has assumed a larger spread of wind speed. New scientific questions are raised in the pursuit of statistical dynamical understanding of meteorological variables in the tropics.
Manipulating marine stratocumulus cloud amount and albedo: a process-modelling study of aerosol-cloud-precipitation interactions in response to injection of cloud condensation nuclei

We use a cloud-system-resolving model to study marine-cloud brightening. We examine how injected aerosol particles that act as cloud condensation nuclei (CCN) are transported within the marine boundary layer and how the additional particles in clouds impact cloud microphysical processes, and feedback on dynamics. Results show that the effectiveness of cloud brightening depends strongly on meteorological and background aerosol conditions. Cloud albedo enhancement is very effective in a weakly precipitating boundary layer and in CCN-limited conditions preceded by heavy and/or persistent precipitation. The additional CCN help sustain cloud water by weakening the precipitation substantially in the former case and preventing the boundary layer from collapse in the latter. For a given amount of injected CCN, the injection method (i.e., number and distribution of sprayers) is critical to the spatial distribution of these CCN. Both the areal coverage and the number concentration of injected particles are key players but neither one always emerges as more important than the other. The same amount of injected material is much less effective in either strongly precipitating clouds or polluted clouds, and it is ineffective in a relatively dry boundary layer that supports clouds of low liquid water path. In the polluted case and "dry" case, the CCN injection increases drop number concentration but lowers supersaturation and liquid water path. As a result, the cloud experiences very weak albedo enhancement, regardless of the injection method.
Heterogeneous freezing of water droplets containing kaolinite particles

Clouds composed of both ice particles and supercooled liquid water droplets exist at temperatures above ~236 K. These mixed phase clouds, which strongly impact climate, are very sensitive to the presence of solid particles that can catalyse freezing. In this paper we describe experiments to determine the conditions at which the clay mineral kaolinite nucleates ice when immersed within water droplets. These are the first immersion mode experiments in which the ice nucleating ability of kaolinite has been determined as a function of clay surface area, cooling rate and also at constant temperatures. Water droplets containing a known amount of clay mineral were supported on a hydrophobic surface and cooled at rates of between 0.8 and 10 K min−1 or held at constant sub-zero temperatures. The time and temperature at which individual 10–50 μm diameter droplets froze were determined by optical microscopy. For a cooling rate of 10 K min−1, the median nucleation temperature of 10–40 μm diameter droplets increased from close to the homogeneous nucleation limit (236 K) to 240.8 ± 0.6 K as the concentration of kaolinite in the droplets was increased from 0.005 wt% to 1 wt%. This data shows that the probability of freezing scales with surface area of the kaolinite inclusions. We also show that at a constant temperature the number of liquid droplets decreases exponentially as they freeze over time. The constant cooling rate experiments are consistent with the stochastic, singular and modified singular descriptions of heterogeneous nucleation; however, freezing during cooling and at constant temperature can be reconciled best with the stochastic approach. We report temperature dependent nucleation rate coefficients (nucleation events per unit time per unit area) for kaolinite and present a general parameterisation for immersion nucleation which may be suitable for cloud modelling once nucleation by other important ice nucleating species is quantified in the future.
Hygroscopic properties of atmospheric aerosol particles over the Eastern Mediterranean: implications for regional direct radiative forcing under clean and polluted conditions

This work examines the effect of direct radiative forcing of aerosols in the eastern Mediterranean troposphere as a function of air mass composition, particle size distribution and hygroscopicity, and relative humidity (RH). During intensive field measurements on the island of Crete, Greece, the hygroscopic properties of atmospheric particles were determined using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Hygroscopicity Differential Mobility Analyzer-Aerodynamic Particle Sizer (H-DMA-APS). Similar to former studies, the H-TDMA identified three hygroscopic sub-fractions of particles in the sub-μm range: a more hygroscopic group, a less hygroscopic group and a nearly hydrophobic particle group. The average hygroscopic particle growth factors at 90 % RH were a significant function of particle mobility diameter (Dp): 1.42 (± 0.05) at 30 nm compared to 1.63 (± 0.07) at 250 nm. The H-DMA-APS identified up to three hygroscopic sub-fractions at mobility diameters of 1.0 and 1.2 μm. The data recorded between 12 August and 20 October 2005 were classified into four distinct synoptic-scale air mass types distinguishing between different regions of origin (western Mediterranean vs. the Aegean Sea) as well as the degree of continental pollution (marine vs. continentally influenced). The hygroscopic properties of particles with diameter Dp≥150 nm showed the most pronounced dependency on air mass origin, with growth factors in marine air masses exceeding those in continentally influenced air masses. Particle size distributions and hygroscopic growth factors were used to calculate aerosol light scattering coefficients at ambient RH using a Mie model. A main result was the pronounced enhancement of particle scattering over the eastern Mediterranean due to hygroscopic growth, both in the marine and continentally influenced air masses. When RH reached its summer daytime values around 70–80 %, up to 50–70 % of the calculated visibility reduction was due to the hygroscopic growth of the particles by water compared to the effect of the dry particles alone. The estimated aerosol direct radiative forcings for both, marine and continentally influenced air masses were negative indicating a net cooling of the atmosphere due to the aerosol. The radiative forcing ΔFr was nevertheless governed by the total aerosol concentration most of the time: ΔFr was typically more negative for continentally influenced aerosols (ca. −4 W m−2) compared to rather clean marine aerosols (ca. −1.5 W m−2). When RH occasionally reached 90 % in marine air masses, ΔFr even reached values down to −7 W m−2. Our results emphasize, on the basis of explicit particle hygroscopicity measurements, the relevance of ambient RH for the radiative forcing of regional atmospheres.
Size distribution of alkyl amines in continental particulate matter and their online detection in the gas and particle phase

An ion chromatographic method is described for the quantification of the simple alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA) and triethylamine (TEA), in the ambient atmosphere. Limits of detection (3σ) are in the tens of pmol range for all of these amines, and good resolution is achieved for all compounds except for TMA and DEA. The technique was applied to the analysis of time-integrated samples collected using a micro-orifice uniform deposition impactor (MOUDI) with ten stages for size resolution of particles with aerodynamic diameters between 56 nm and 18 μm. In eight samples from urban and rural continental airmasses, the mass loading of amines consistently maximized on the stage corresponding to particles with aerodynamic diameters between 320 and 560 nm. The molar ratio of amines to ammonium (R3NH+/NH4+) in fine aerosol ranged between 0.005 and 0.2, and maximized for the smallest particle sizes. The size-dependence of the R3NH+/NH4+ ratio indicates differences in the relative importance of the processes leading to the incorporation of amines and ammonia into secondary particles. The technique was also used to make simultaneous hourly online measurements of amines in the gas phase and in fine particulate matter using an Ambient Ion Monitor Ion Chromatograph (AIM-IC). During a ten day campaign in downtown Toronto, DMA, TMA + DEA, and TEA were observed to range from below detection limit to 2.7 ppt in the gas phase. In the particle phase, MAH+ and TMAH+ + DEAH+ were observed to range from below detection limit up to 15 ng m−3. The presence of detectable levels of amines in the particle phase corresponded to periods with higher relative humidity and higher mass loadings of nitrate. While the hourly measurements made using the AIM-IC provide data that can be used to evaluate the application of gas-particle partitioning models to amines, the strong size-dependence of the R3NH+/NH4+ ratio indicates that using bulk measurements may not be appropriate.
Regional scale effects of the aerosol cloud interaction simulated with an online coupled comprehensive chemistry model

We have extended the coupled mesoscale atmosphere and chemistry model COSMO-ART to account for the transformation of aerosol particles into cloud condensation nuclei and to quantify their interaction with warm cloud microphysics on the regional scale. The new model system aims to fill the gap between cloud resolving models and global scale models. It represents the very complex microscale aerosol and cloud physics as detailed as possible, whereas the continental domain size and efficient codes will allow for both studying weather and regional climate. The model system is applied in a first extended case study for Europe for a cloudy five day period in August 2005. The model results show that the mean cloud droplet number concentration of clouds is correlated with the structure of the terrain, and we present a terrain slope parameter TS to classify this dependency. We propose to use this relationship to parameterize the probability density function, PDF, of subgrid-scale cloud updraft velocity in the activation parameterizations of climate models. The simulations show that the presence of cloud condensation nuclei (CCN) and clouds are closely related spatially. We find high aerosol and CCN number concentrations in the vicinity of clouds at high altitudes. The nucleation of secondary particles is enhanced above the clouds. This is caused by an efficient formation of gaseous aerosol precursors above the cloud due to more available radiation, transport of gases in clean air above the cloud, and humid conditions. Therefore the treatment of complex photochemistry is crucial in atmospheric models to simulate the distribution of CCN. The mean cloud droplet number concentration and droplet diameter showed a close link to the change in the aerosol. To quantify the net impact of an aerosol change on the precipitation we calculated the precipitation susceptibility β for the whole model domain over a period of two days with an hourly resolution. The distribution function of β is slightly skewed to positive values and has a mean of 0.23. Clouds with a liquid water path LWP of approximately 0.85 kg m−2 are on average most susceptible to aerosol changes in our simulations with an absolute value of β of 1. The average β for LWP between 0.5 kg m−2 and 1 kg m−2 is approximately 0.4.
Distribution of hydrogen peroxide and formaldehyde over Central Europe during the HOOVER project

In this study we report measurements of hydrogen peroxide (H2O2), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HOx OVer EuRope (HOOVER) project (HOx = OH+HO2). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54° N, 9° E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H2O2 and CH3OOH*. In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H2O2 and CH3OOH* show maxima above the boundary layer at 2–5 km, being more distinct over southern than over northern Europe. We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H2O2. Large uncertainties about retention coefficients and cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H2O2. A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H2O2 as simulations improve significantly with this effect switched off.